Certain alpha-haloaldehyde addition products of ethylenethioureas and process



United States CERTAIN ALPHA-HALOALDEHYDE ADDITION 1 PRODUCTS F ETHYLENETHIOUREAS AND PROCESS Russell M. Bimber, Painesville, Ohio, assignor to Diamond Alkali Company, Cleveland, Ohio, at corpn'ration of Delaware No Drawing. Filed Jan. 27, 1958, Ser. No; 711,130 9 Claims. cl. 260-3096) This invention relates to the reaction of a substituted ethylcnethiourea with an alpha halo aldehyde and to the reaction products and applications thereof.

The term substituted ethylenethiourea as employed in the specification and claims is intended to refer broadly wherein R R R and R are selected from the group consisting of hydrogen atoms, alkyl radicals, such as methyl, ethyl, propyl, butyl, octyl, their isomers and the like, especially lower alkyl radicals; aryl radicals, such as phcnyl radicals and naphthyl radicals; thienyl radicals; e.g.,-C H S; aralkyl radicals, such as benzyl and phen ethyl radicals; alkaryl radicals, such as tolyl and xylyl radicals; and substituted derivatives of these radicals, especially corresponding halogen-substituted group, i.e., chlorine, fluorine, bromine, and iodine substituted derivatives, each of which radicals preferably contains no more than 16 carbon atoms.

The expression alpha halo specification and claims is intended to refer broadly to a compound of the structure:

RCHO

wherein R is an alpha-halogen-substituted alkyl radical, especially a halogen-substituted lower alkyl radical, as previously defined. Exemplary alpha halo aldehydes are 2,2,3 trichloropropionaldehyde; 2,2,3 -tribro1nopropionaldehyde; 2,2,3-trichlorobutraldehyde; 2,3-dichlorobutraldehyde; 2,2,3,3-tetrachlorobutyraldehyde; and 2,2,3-trifiuorobutraldehyde; specifically preferred alpha halo alde-' hydes being alpha halo acetaldehydes, such as chloral; 2,2 dichloroacetaldehyde; 2,2,2 tribromoacetaldehyde'; 2,2-dichloro-2-bromoacetaldehyde: It is also intended that the above alpha halo aldehydes and specifically the alphalhalo acetaldehydes should include their respective hydrates, e.g., chloral hydrate, the hydrate of 2,2,2-trichlorobutr'aldehyde, and the hydrate of 2,2-dichloroi acetaldehyde.

The compounds of this invention have the following structure:

a. in firm-f R| HN N 0 1: Lil-R et 53 1 2 aha 4 re selected from the 70 aldehyde? as used in the' 2,981,739 .7 Patented Apr. 25, 1961 ing halogen-substituted groups; and R is a halogen-substituted lower alkyl radical.

The term 1:1 addition product as employed in the specification and claims is intended to refer to the chemical reaction product formed by the stoichiometric combination of 1 molecule of one reactant with 1 molecule trichloro 1 hydroxyethyl, 2,2,3 trichloro 1 hydroxypropyl, 2,2,2 tribromo 1 hydroxyethyl, 2- chloro 1 hydroxypropyl, and 2 chloro 1 hydroxyethyl, 2,2,3 tribromo 1 hydroxypropyl; 2,2,3 trichloro l hydroxybutyl; 2, 3 dichloro 1 hydroxybutyl; 2,2,3,3 tetrachloro 1 hydroxybutyl; 2,2,3 tri* fluoro 1 hydroxybutyl; 2,2 dichloro 1 hydroxyethyl; and 2 bromo 2,2 dichloro 1 hydroxyethyl.

Specifically, the 1:1 addition product of ethylenethiourea and chloral melts ,at l61-163 C. and, based, on the analytical procedure disclosed by Edens and Johnson, Journal of American Chemical Society, vol. 63, (1941), p. 3527, is represented by the structure:

(I) HzC-CH1 03 Based on the above reference, a compound having the structure 1 4 a HiNi green-Con.

f S f would be expected to give a white gel when mixed with a solution of copper sulfate and hydrochloric acid, whereas a compound of the structure. (I) would not. The product (I) i.e., 2-(2,2,2 trichloro-l-hydroxyethylthio) 2- imidazoline, of the reaction of chloral and ethylenethio urea given above does not give such a gel whereas ethylenethiourea alone does.

Specific reactions. falling within the scope of. this invention are listed in Table I in which compounds in column 1 may be reacted with compounds in column 2.

In certain instances, the easily effected by bringing the two reactants together in the presence of a solvent such as water or an organic liquid, e.g., benzene, chloroform, heptane, trichlorobenzene, or the like. Typically the reactions are exothermic and are desirably carried outat a temperature within the range from about 0 to 0., preferably below the reflux temperature of the aldehyde, e.g., usin chloral below about 97 C. In general, itis 'pi'efe'rredtb employ above reactions may be more substantially stoichiometric ratios of the reactants, however, considerable departure from these ratios can be tolerated in many instances without serious detriment to either yields or quality of product. The reaction is preferably carried to completion which generally requires not more than about 2 hours, e.g;, 1-2 hours at 90 C.

The compounds of this invention are useful in the fields of pharmaceuticals, chemical intermediates, and also show biological activity, such as the control of microorganism growth, e.g., protection of tomato foliage against blight fungi, the prevention of undesirable plant growth, the control of insect growth, i.e., the control of aphid growth.

While compounds of this invention may be employed in a variety of applications, biological or'otberwise, it will be understood, of course, that these compounds may be utilized in diverse formulations, both liquid and solid, including finely-divided powders and granular materials, as well as liquids, such as salt solutions, concentrates, emulsifiable concentrates, slurries and the like. depending upon the application intended and the formulation media desired.

Thus, it will be appreciated that compounds of this invention may be employed to form biologically active substances containing such compounds as essential active ingredients thereof, which compositions may also include finely-divided dry or liquid diluents, extenders, fillers, conditioners, including various clays, diatomaceous earth, talc, spent catalyst, alumina-silica materials and incorporating liquids, solvents, etc., typically water and various organic liquids such as kerosene, benzene, toluene and other petroleum distillate fractions or mixtures thereof.

When liquid formulations are employed, or dry materials prepared which are to be used in liquid form, it is desirable in certain instances additionally to employ a wetting, emulsifying, or dispersing agent to facilitate use of the formulation, e.g., Triton X-155 (alkyl aryl polyether alcohol, US. Patent 2,504,064). Suitable surface active agents are set forth in an article by McCutcheon in' Example I 40.8 g. (0.4 mol) ethylenethiourea and 135.0 g. (0.8 mol) chloral hydrate are dissolved in 400 ml. of H containing 4.0 mol. concentrated HCl. The clear solution is filtered and heated in a boiling water bath for 1 hour and 45 minutes after which it is allowed to cool. Upon cooling, filtering, washing several times with distilled water, and drying at 50 C. a product consisting of white flakes is obtained. This product melts at 16l-.

163 C. with decomposition above this range. Preparation of the desired reaction product, C H Cl N OS; is indicated through the following elemental analytical data:

Insecticidal activity is shown in using the bean aphid, Aphis fabae, which is'cultured on nasturtium plants.

4 Nasturtium plants are infested with approximately 100 aphids at the time of treatment. The test plants are treated separately by pouring formulations (2000 p.p.m. product of Example I, 5% acetone, 0.01% Triton X-155,

5 balance water) on the soil at rates equivalent to 64 lbs./ acre and 32 lbs./ acre. Mortality observations 24 hours after treatment show 97% and 69% mortality at 64 and 32 lbs/acre, respectively.

Example III Example IV A tomato foilage disease test is conducted measuring the ability of the test compound to protect tomato foilage against infection by the early blight fungus, Alternaria solani. Tomato plants 5 to 7 inches high of the variety Bonny Best are employed. The plants are sprayed with 100 ml. test formulation (2000 p.p.m. and 400 p.p.m. product of Example I in combination with 5% acetone, 0.01% Triton X-l55, and the balance water) at 40 lbs. air pressure while being rotated on a turntable in a spray chamber. After the spray deposit is dry, the treated plants, and comparable untreated controls, are sprayed with approximately 20 ml. of a spore suspension containing about 20,000 conidia of A. solani per ml. The plants are held in a saturated atmosphere for 24 hours at 70 F. to permit spore germination and infection. After 2 to 4 days, lesion counts are made on the three uppermost fully expanded leaves. Data based on the number of lesions obtained on the control plants shows significant disease control.

Example V To evaluate herbicidalactivity, seeds of perennial rye grass are treated in Petri dishes withaqueous suspensions of the product of Example I at 1000 and l00p.p.m. (1000 or 100 p.p.m. product of Example I, 5% acetone, 0.01% Triton X-l55, thebalance water). seeds are scattered in separate dishes containing filter paper discs moistened with 5 ml. of the test formulation at each concentration. After 7 to 10 days under controlled conditions, the test compound is given arating which corresponds to the concentration that inhibits germination of half the seedsof the test.crop. Employing this procedure, results indicate a concentration of about 100-1000 p.p.m. inhibit seed germination.

Example VI Further to evaluate the effect'of the product of Example I upon the germination of seeds in soil, a mixture of seeds of six crop plants is broadcast in 8" x 8" x 2" metal cake pans filled to within one half inch of the top with composted greenhouse soil. The seed-is uniformly covered with about one-quarter inch soil and 5 then watered. After 24 hours, 80 ml. of an aqueous test formulation containing 320 mg. product of Example I is sprayed at l0'lbs. air pressure uniformly over the surface of the pan. This is equivalent to 64 lbs/acre. The seed mixture contains seeds of three broadleafs: turnip, flax, and alfalfa, and three grasses: wheat, millet, and rye grass. Two weeks after treatment, records are taken on seedling stand as compared to the controls. Using this procedure, results show 60% stand of the broadleaf and 20% stand of the grasses. The grasses 75 however are severly stunted and receive phytotoxicity rat- Lots of 25.

ing of 9 based on a scale from 0 for no iniury to 11 for plant kill.

It is to be understood that although the invention has been described with specific reference to particular embodiments thereof, it is not to be so limited, since changes 6 and alterations therein may be made which are within the full intended scope of this invention as defined by the appended claims.

What is claimed is:

1. The method which comprises chemically reacting ethylenethiourea and chloral.

2. The method which comprises chemically reacting ethylenethiourea and chloral hydrate.

3. The method which comprises chemically reacting 1 molecule of ethylenethiourea with 1 molecule of chloral yielding a product melting at 161-163 C.

4. The method which comprises chemically reacting 1 molecule of ethylenethiourea with 1 molecule of chloral hydrate.

5. The method which comprises chemically reacting 1 molecule of ethylenethiourea with 1 molecule of chloral yielding a product melting at 161-163 C. wherein the reaction is carried out in the presence of water from 0 to 150 C.

6. The method which comprises chemically reacting 1 molecule of ethylenethiourea with 1 molecule of chloral hydrate wherein the reaction is carried out in the presence of water below 150 C.

7. A compound having the structure wherein R R R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl, naphthyl, thienyl, benzyl, phenethyl, tolyl, xylyl and corresponding halogen-substituted groups; and R is a halogen-substituted lower alkyl, said i -C-R H group being derived from an alpha halo aldehyde.

6 8. The compound 2-(2,2,2-trichloro-l-hydroxyethylthio)-2-imidazoline.

9. The method which comprises chemically combining an ethylenethiourea having the structure wherein R R R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl, naphthyl, thienyl, benzyl, phenethyl, tolyl, xylyl and corresponding halogen-substituted groups; with an alpha halo aldehyde having the structure RCHO, wherein R is an alpha halogen-substituted lower alkyl radical, to produce a product having the structure wherein R R R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl, naphthyl, thienyl, benzyl, phenethyl, tolyl, xylyl and corresponding halogen-substituted groups; and R is a halogen-substituted lower alkyl radical.

References Cited in the file of this patent UNITED STATES PATENTS 2,353,997 Cooper July 18, 1944 2,357,149 Kamp Aug. 29, 1944 2,621,211 Behnisch Dec. 9, 1952 2,635,115 Bernstein Apr. 14, 1953 2,726,150 Wolter Dec. 6, 1955 2,764,478 Searle Sept. 25, 1956 2,774,706 Hackmann Dec. 18, 1956 2,801,200 Hackmann July 30, 1957 

7. A COMPOUND HAVING THE STRUCTURE 